Chlorination of ketonic acetyl groups

ABSTRACT

R3PCl2 converts the carbonyl group of ketones to chlorine containing groups which, combined with dehydrochlorination methods, provides a new synthetic route for the production of acetylenic compounds useful for making polymers. The R3PO produced in the reaction is reconverted to R3PCl2 by reaction with phosgene thus providing an economical process for converting ketones to chlorine derivatives and from thence to acetylenic derivatives. Each R is C1 20 alkyl, phenyl, lower alkylphenyl, halophenyl, phenoxyphenyl or naphthyl.

United States Patent n91 Relles v 1 1 Feb. 6, 1973 CHLORINATION OFKETONIC ACETYL GROUPS [75] Inventor: Howard M. Relles, Saratoga, N .Y.[73] Assignee: General Electric Company [22] Filed: March 1, 1971 [21]Appl.'No,: 119,839

Related US. Application Data 7 [63'] Continuation-impart of Ser, No.67,211, Aug. 26,

1970, abandoned.

[52] Cl..; ..260/668 R, 260/650 R, 260/65] R, I 260/654 D [51] Int.Cl..... ..C07c 15/04 [58 Field of Search. #1....260/651 HA,

[56] v References Cited UNITED STATES PATENTS 3,206,516 9/1965Ziegenbein et al 260/654 dehydrochlorination Primary Examiner-Curtis R.Davis Attorney-James W. Underwood, Joseph T. Cohen,

Paul A. Frank, Charles T. Watts, Frank L. Neuhauser, Oscar B. Waddelland Joseph B. Forman 5 7] ABSTRACT R PCl converts the carbonyl group ofketones to chlorine containing groups which, combined with methods,provides a new synthetic route for the production of acetyleniccompounds useful for making polymers. The R PO produced in the reactionis reconverted to R PC1 by reaction with phosgene thus providing aneconomical process for converting ketones to chlorine derivatives andfrom thence to acetylenic derivatives. Each R is C alkyl, phenyl, loweralkylphenyl, halophenyl, phenoxyphenyl or naphthyl.

18 Claims, No Drawings This application is a continuation-in-part of mycopending, but subsequently abandoned application, Ser. No. 67,2l l,filed Augs26, 1970, and assigned to the same assigneeasthepresen'tappli'cation.

This invention relates to an improved process for converting the ketonicacetyl grou'p' to chlorine containing substituerits. This inventionfurther contemplates the process wherein the chlorine substituents aredehydrohaloge'nated to the corresponding acetylenic groups and furtherc'o'ntemplatesa process whereby only phosgene and the ke-bone need to besupplied to the reaction which produces the chlorinated derivativestherebyenablingsuch chlorine-containing derivatives to be made in acontinuous process. More particularly, this invention relates to theconversion of the ketonic acetyl group of methyl ketones, i.e., ketoneswhere the acetyl group ((1 thi is the ketonic moiety tochlorinecontaining substituents selected from the group consisting ofaaand a-chloroethylidene a-chlorovinyl and to the dehydro-halogenationof these chlorine-containing substituents to the correspondingacetylenic group. The balance of the ketonic moiety can be any aliphaticor aromatic hydrocarbon or halohydrocarbon, or any aryl or haloarylether, i.e., the ether oxygen is directly bonded to a carbon atom in anaromatic ring.

Polymeric acetylenes and a process for producing the same are disclosedin U.S. Pat. No. 3,300,456- Allan S. Hay. The polymers and copolymers ofdiethynyl compounds are an extremely interesting group of polymers sincethey contain a very high percentage by weight of carbon, for example,the polymers and copolymers from diethynylbenzenes contain over 90percent by weight carbon. The monoethynyl compounds, for example,methylacetylene, phenylacetylene, etc., can be used as chain-stoppers toregulate the molecular weight of the polymers and copolymers fromdiethynyl compounds. Furthermore, the monoand diethynyl compounds areuseful for making photosensitive compositions as disclosed in thecopending application of Allan S. Hay, Ser. No. 764,287, filed now U.S.Pat. No. 3,594,175 Oct. 1, 1968 and assigned to the same assignee as thepresent invention.

Because ofthe wide utility of the acetylen'ic polymers and copolymers asdisclosed the aforementioned patents, it would be highly desirable tohave an economical process for producing the acetylenic compoundsrequired as starting materials for the polymers and for thechain-terminating, molecular weight regulators.

Generally, ketones react with ha'logenating agents to producehaloketones, for example, acetone reacts with ha'logenating agents toproduce a-haloac'etone. Unlike phosphorus pentabromide which brominatesketones to give a-bromoketones, phosphorus pentachloride reacts withketones to p-roduce predominantly the gemdic-hloride wherein twochlorines replace the oxygen of the ketone. Some chloro-olefins andhydrogen chloride as well as other products (vide infra) are alsoproduced. in the case of mixed aryl alkyl ketones, i.e., the ketoniccarbonyl group is between an aryl and alkyl group, the a-chloroolefinsare generally the chief product. in the case of dialkyl ketones, thedehydrohalogenation reaction can involve either or both alkyl groups.Since the gem-dichlorides and the chloroolefins can be readilydehydro'halongenated to the corresponding acetylenic compounds, themixture does not have to be separated prior to dehydrohalogenation.

From a laboratory preparation standpoint, the use of phosphoruspentachloride for producing the chloro derivatives followed bydehydrohalogenation is a satisfactory method for converting ketones tothe corresponding acetylenes, see for example, Chapter I titledSynthesis of Acetylenes, written by Thomas L. Jacobs in Volume 5 ofOrganic Reactions, John Wiley & Sons, Inc., New York (1949) and thereferences cited therein and Methods 43 and 72 and the literaturereferences cited therein in the book Synthetic Organic Chemistry byRomeo B. Wagner and Harry D. Zook, John Wiley & Sons, Inc., New York(1953). Unfortunately, because of the high cost of phosphoruspentachloride since only two out of the five chlorines can be utilizedin the chlorination reaction, because of complicating side reactions,and because the resulting phosphorus oxychloride cannot be readilyreconverted to phosphorus pentachloride (see for example, U.S. Pat No.2,907,798 and German patent 492,061), this method is too expensive to becommercially feasible for the conversion of ketonic acetyl compounds totheir corresponding gem-dichloroethyl and chloroethylenic derivativesuseful as intermediates for preparing acetylenic derivatives.

German patent 1,192,205 discloses that phosgene or thionyl chloride willreact with triphenylphosphine oxide to producedichlorotriphenylphosphorane. Other aryl groups can be substituted forthe phenyl group and triphenylarsine oxide and triphenylstibene oxidecan be substituted for the triphenylphosphine oxide. Horner et al.,Liebigs Ann. 626, 26 (l959) prepared dichlorotriphenylphosphorane byreaction of chlor ne with triphenylphosphine. They found that asuspension of dichlorotriphenylphosphorane in refluxing benzene, in thepresence of triethylamine, reacted with benzaldehyde to produce a 59percent yield of benzal chloride or with cyclohexanone to produce a 45percent yield of l-chloro-cyclohexene. However, Francis Freenor, III, inhis Ph.D. thesis, Ether Cleavage by Triphenylphosphine Dibromide andRelated Reactions," Disseration 68l2,689 University Microfilms, lnc.,Ann Arbor (1968), reports that no volatile products are obtained fromthe reaction of either cyclohexanone or acetone with triphenylophosphinedibromide (dibromotriphenylphosphorane) in N,N-

dimethylformamide, even when heated, but that the ketone was consumed.It is not self-evident whether the difference between the results ofFreenor and Horner et al. with cyclohexanone is due to the differenthalogen in the phosphorane or the lack of triethylamine in the Freenorreaction.

Insofar as I am aware, the only reaction of phosgene directly with aketone at room temperature was reported by Matuszak in J. Am. Chem.Soc., 56, 2007 (1934). He did not identify the compound which heobtained but stated that the properties which he did determinecorresponded more closely to those which might be expected forisopropenyl-chloroformate than to other possible products. This compoundwould be the chloroformate ester of the enol form of acetone. Even atelevated temperatures, phosgene does not react with ketones to replacethe carbonyl oxygen with halogen as does occur in the reaction withphosphorus pentachloride. Instead, aldol type condensations occurleading to a mixture of complex products.

Because phosgene is readily'available in large commercial quantities ata very low price, is an easily handled gas despite its toxicity, and isnot nearly as vigorous in its reactions as is gaseous chlorine, etc., itwould be highly desirable to use this material as a cheap and easilyuseable source of chlorine in the conversion of ketonic acetyl groups tothe above-mentioned halo groups to produce intermediates which can bedehydrohalogenated to their corresponding acetylenic derivatives.Unexpectedly, I have found that although phosgene cannot be useddirectly, dichlorophosphoranes having the formula R PCl obtained by thereaction of phosgene with phosphine oxides having the formula R PO, canbe used to convert ketonic acetyl groups to a,a-dichloroethyl groups,achlorovinyl groups and a-chloroethylidene groups. In the aboveformulas, each R is independently selected from the group consisting ofC alkyl, phenyl, lower alkyl substituted phenyl, halophenyl,phenoxyphenyl and naphthyl. It is to be understood that the termsdichlorophosphorane(s)" and phosphine oxide(s) used hereinafter forbrevity, will refer to the compounds having the above formulas.

Typical examples of the C alkyl groups which R can be are methyl, ethyl,propyl, isopropyl, the various butyl isomers, e.g., n-butyl, sec-butyl,tert-butyl, etc., the various amyl isomers, the various hexyl isomers,including cyclohexyl, the various heptyl isomers, the various octylisomers, the various decyl isomers, the various dodecylisomers, thevarious octadecyl isomers, the various eicosyl isomers, etc. The loweralkyl substituted phenyl groups can be a phenyl group having from one tofive, preferably one to two, lower alkyl substituents, e.g., any of theabove C alkyl groups. The halophenyl groups can be a phenyl group havingfrom one to five, preferably one to two halogens substituted on thephenyl nucleus, e.g., chlorine, bromine, iodine, fluorine, preferablychlorine. Preferably the phenoxyphenyl groups are those in which thephenyl group has one phenoxysubstituent. However, from two to five suchsubstituents may be present, if desired.

The chlorine containing substituent produced, of those named above, isdependent on the nature of the ketone, and to some extent on thereaction conditions. These are not critical parameters, since they arewithin the knowledge and control of a skilled person carrying out thereaction and furthermore, all three of these chlorinated groups can beconverted to their corresponding acetylenic groups with the use ofdehydrohalogenating agents under dehydrohalogenating conditions. Hereagain, as is well known in the art, the particular dehydrohalogenatingagents chosen can influence the actual position of the acetylenic group,i.e., whether it is a terminal acetylenic group or between the secondand third carbon atom of an alkyl chain.

When the ketone is an acetyl substituted aromatic compound, for exampleacetophenone, diacetylbenzene, acetyl-naphthalene, p-chloroacetophenone,acetyldiphenyl ether (phenoxyacetophenone), diacetyldiphenyl either,etc., the acetyl groups will be converted by reaction with thedichlorophosphorane to a mixture of a-chlorovinyl and a,a-dichloroethylgroups with the former predominating. Because the aryl substituent isdirectly attached to the ketonic carbonyl group, it is impossible forthe a-chloroethylidene group to form with these ketones. When the ketoneis an acetyl substituted aliphatic compound, all three groups can and doform except in the case of acetone where of course it is impossible toform other than the a,a-dichloroethyl and a-chlorovinyl derivatives. Inthis respect, the chlorine compounds formed are the same, but notnecessarily in the same proportion, as would be formed if phosphoruspentachloride had been used as the chlorinating agent. The course ofthis reaction, is extremely well documented and the course of myreaction with aliphatic ketones will be readily apparent to thoseskilled in the art based on this known reaction with phosphoruspentachloride. However, the yield of the desired chlorinated products isessentially quantitative in my reaction based on the amount of ketoneconsumed with no evidence of any by-products. In marked contrast, thereaction with phosphorus pentachloride gives low yields of the desiredchlorinated products, in the range of 40-60 weight percent based on theamount of ketone consumed, and considerable amounts of undesirableby-products, especially chlorinated ketones resulting from chlorinationof the alkyl group rather than the ketonic carbonyl group, and aldolcondensation products arising because of the acidity of the phosphorusoxychloride produced, etc. The diverse and complex nature of thecomposition of the reaction mixture makes separation of the desiredchlorinated compounds from the undesirable by-products extremelydifficult.

My reaction can be carried out 'at ambient temperature and at ambientpressure if desired, but is speeded up by heating at elevatedtemperatures. In the case of lower aliphatic ketones, for'exampleacetone, methyl ethyl ketone, etc., where the monochlorovinyl compoundsproduced are extremely volatile because of their very low boiling point,it is desirable to carry out the reaction at room temperature unlessprovision is made for sufficient cooling capacity and low enough not aproblem, the reaction can be hastened by heating up to the refluxtemperature of the reaction mixture at or above atmospheric pressure. 7

The reaction between the phosphine oxide and phosgene to produce thedichlorophosphorane is greatly hastened if a solvent for the phosphineoxide is used. The solvent, of course, should be inert and nonreactivewith phosgene, the phosphine oxide or the dichlorophosphorane productand liquid at the temperature at which it is used in the process. Highlypolar solvents are required to dissolve the phosphine oxides. Typicalsolvents which I can use are the nitriles, for example acetonitrile,propionitrile, butyronitrile, benzonitrile, etc., or the halogenatedhydrocarbons, for example chloroform, trichloroethylene, chlorinatedbenzenes, chlorinated biphenyls, chlorinated diphenyl ethers, etc. Aswill be explained later, acetonitrile is an ideal solvent to. be used.Mixtures of these solvents or mixtures of one or more of these solventswith other liquids which are not solvents or only poor solvents can alsobe used.

The solubility of both the phosphine oxide and the dichlorophosphoranein a particular solvent is dependent on the particular R substituentsand the temperature. In general, a phosphorane is more soluble than itscorresponding phosphine oxide. Either of these compounds having alkyl,phenyl, phenoxyphenyl or alkyl substituted phenyl substituents are moresoluble than those having halophenyl substituents which in turn are moresoluble than those having naphthyl substituents. Heating increases thesolubility of all of these compounds in a particular solvent.

As will be more evident later, complete solubility of the phosphineoxide and its corresponding dichlorophosphorane at room temperature isdesirable, but not necessary. Those phosphine oxides and phosphoraneswhich are less soluble require a greater amount of solvent, heating orboth to dissolve a given amount. The speed of reaction of the phosphineoxide with phosgene and of the dichlorophosphorane with the ketone isincreased by having the'r'eaction mixture homogeneous, by increasing theconcentration of the reactants dissolved in the reaction mixture and byheating the reaction mixture.

As will be shown in the specific examples, another factor governing therate of reaction of the dichlorophosphorane with ketones is the natureof the substituents. Electron donating substituents decrease the ratewhile electron withdrawing substituents increase the rate of reaction.This is true even for substituents on the arylnucleus of a substituent.For exam ple, alkyl groups,- either directly attached to the phosphorusatom or as a substituent on an aryl nucleus which is attached to thephosphorus atom (e.g., alkylphenyl), alkoxy and aryloxy substituents onthe aryl nucleus, etc., reduce the rate compared withdichlorotriphenylphosphorane, whereas halo substituents on the arylnucleus increase the rate of reaction of the correspondingdichlorophosphoranes.

By taking advantage of one or more of the above factors, the optimumreaction conditions for any of the above phosphine oxides ordichlorophosphoranes can be readily attained. Consideration of the samefactors also leads to the conclusion that triarylphosphine oxides anddiclorortriarylphosphoranes, wherein the aryl nuclei are unsubstitutedor halo substituted, will be the preferred species of reactants.Although dichlorotriphenylphosphorane is less reactive with ketones thanthe same phosphorane where one or more of the phenyl substituents haveone or more halo substituents, this difference in reactivity is easilycompensated for by using a higher reaction temperature. For example,using acetonitrile as the solvent, at C. under the autogeneous pressureof the reaction mixture, the reaction of dichlorotriphenylphosphoranewith various ketones is complete in one hour. The solubilities of bothtriphenyl-phosphine oxide and dichlorotriphenylphosphorane in all of thesuitable solvents are greater than the solubilities of their halophenylanalogues. This not only permits more concentrated, homogeneoussolutions to be used at a given temperature, which can also be used tocompensate for the slower reaction rate, but also permits cooling of thereaction mixture to room temperature after reaction with the ketonewithout precipitation of the triphenylphosphine oxide. This greatly aidsin the separation of the chlorinated products from the balance of thereaction mixture, especially in the extraction procedure to be discussedlater, because of the relatively low boiling points of the extractants.A homogeneous reaction mixture is desirable at all times during thecontinuous process to be described hereinafter. Therefore,triphenylphosphine oxide and dichlorotriphenylphosphorane are preferredover their halophenyl analogues.

The reaction between phosgene and the phosphine oxide produces carbondioxide. The evolution of carbon dioxide can be used as a monitor todetect when sufficient phosgene has been introduced into the reactionmixture to convert all of the phosphine oxide to thedichlorophosphorane. Alternatively, this can be followed bydetermination of the amount of phosgene introduced by use of aflowmeter, by weight difference of either the reaction mixture or thephosgene container, etc. This reaction is exothermic and therefore it isgenerally desirable to provide cooling during the phosgene addition orto introduce the phosgene at a rate designed to control the exothermicreaction. Since phosgene itself, if present, will cause undesirable sidereactions with the ketones at elevated temperatures, any excess phosgeneintroduced in making the dichlorophosphorane should be removed eitherbefore the introduction of the ketonic acetyl compound or the equipmentused should permit the phosgene to escape from the reaction mixture asit is heated, if elevated.

temperatures are to be used for the reaction between thedichlorophosphorane and the ketonic acetyl compounds. In either case,phosgene is easily removed by refluxing the reaction mixture with awater-cooled condenser open to the atmosphere, preferable through adrying tube, since under these conditions the phosgene will escape.Alternatively, the excess phosgene can be removed by a flow of inert gasthrough the reaction medium. Dry air or nitrogen is conveniently usedfor this purpose.

In the reaction between the dichlorophosphorane and the ketonic acetylcompound, dichlorophosphorane is converted to the correspondingphosphine oxide which can be separated from the chlorinated reactionproducts and reacted with an additional amount of phosgene permittingits reuse in the process. I have discovered a convenient means of doingthis by using acetonitrile as the solvent for the phosphine oxideinitially in the reaction with phosgene, as well as the reaction betweenthe dichlorophosphorane and the ketonic acetyl compound.

Acetonitrile is immiscible with liquid alkanes, for example pentane,hexane, heptane, the various petroleum fractions known as petroleumethers, etc. and is heavier so that it forms the lower layer when mixedwith them. These liquid alkanes are good solvents for the chlorinatedreaction products but are very poor solvents for the phosphine oxides.They can be used therefore to extract the desired reaction products fromthe reaction mixture, leaving essentially all of the phosphine oxidedissolved or as a precipitate in the acetonitrile layer. Theacetonitrile layer and the phosphine oxide is recycled back to theinitial step in the process and reacted with phosgene. The desiredchlorinated products are readily separated from the liquid alkane layerby fractional distillation permitting the liquid alkane to be recycledto the extraction step. By this scheme, 1 have provided a continuousprocess for conversion of the ketonic acetyl compounds to theirchlorinated products with only phosgene and the ketonic acetyl compoundbeing consumed in the reaction with the capability of recovering andreusing the other materials.

It will be readily apparent that if a precipitate of phosphine oxide ispresent in the acetonitrile layer, that it is more difficult to performthe above-described extraction step than if no precipitate were present.This is especially true in the continuous process where the precipitatewould necessitate the return of both the acetonitrile and theprecipitated phosphine oxide back to the reactor for reaction withphosgene. Transfers of such as a slurry can be done, but not asconveniently as when a homogeneous solution is transferred.

in a few cases, where aliphatic ketones are chlorinated by my process,the chlorinated products are the most volatile component of the reactionmixture, in fact some are gases at room temperature and atmosphericpressure. In these cases, no extraction step is required since the gasescan be condensed as they autogeneously distill from the reaction mixtureand the liquid products can be distilled from the balance of thereaction mixture. The reaction should be run so as to convert all of theketone to chlorinated products so that the residual reaction mixturewill contain only the solvent, the phosphine oxide and any excessdichlorophosphorane that was present. Since my reaction produces noby-products which I have been able to detect, the residual reactionmixture, without further treatment is ready to be reacted with phosgeneand reused in my process. Under these conditions, it does not matterwhether some of the phosphine oxide precipitates from the reactionmixture.

Although only one mole of dichlorophosphorane is required for eachequivalent of ketonic acetyl groups, I have found that there areadvantages to using an excess of the dichlorophosphorane. One advantageis that the reaction with the ketone is hastened to completion. Anotheris that the excess dichlorophosphorane, like the phosphine oxide,remains with the acetonitrile in the above-described continuous processand increases the amount of phosphine oxide which can be dissolved for agiven volume of acetonitrile. The excess amount, once supplied, is notlost in the reaction but is recycled back to the starting point alongwith the phosphine oxide produced in the ketone reaction. For thesereasons, I prefer to use an excess dichlorophosphorane and generallyprefer to use up to 2 or more moles of dichlorophosphorane for eachequivalent of ketonic acetyl group in the compound.

The chloro compounds prepared by my reaction are readilydehydrohalongenated with a wide variety of dehydrohalogenating agentswell-known to be capable of dehydrohalogenating both dihaloalkanes andhalooletins to acetylenes when used under their knowndehydrohalogenating conditions. These may be aqueous or organic solventsolutions or suspensions of alkali metal hydroxides, alkali metalalkoxides, alkali metal alkyls, alkali metal aryls, alkali metal amideseither as suspensions in organic liquids or in liquid ammonia, etc.

As is evident to those skilled in the art, the dehydrohalogenation of ana-chlorovinyl group can proceed in different ways depending on thenature of the carbon atom to which the a-chlorovinyl group is attached.If it is attached to an aromatic carbon atom, then only thecorresponding ethynyl derivative will be produced, i.e.,dehydrohalogenation of a-chlorovinylbenzene, also known asa-chlorostyrene, only produces phenylacetylene. However, if thea-chlorovinyl group is on an aliphatic carbon atom, also having ahydrogen atom on it, the dehydrohalogenation can lead to two products,either the corresponding ethynyl compound or the corresponding allene l,Z-diene) derivative.

Dehydrohalogenation of the a,a-dichloroethyl groups follows the samepath as dehydrohalogenation of the a-chlorovinyl group. As explainedpreviously, dehydrohalogenation of the a-chloroethylidene group isconfined to those chloro compounds arising out of the reaction ofaliphatic ketones. Dehydrohalogenation of these compounds produceseither an acetylenic compound where the acetylenic bond is between thesecond and third carbon atom, or a l,2-diene structure.

In those cases, where two dehydrohalogenation products are possible, theactual product is a mixture of the two with the ratio of the two beingdependent on the particular dehydrohalogenating agent used and theparticular dehydrohalogenation conditions. Generally, alkali metalhydroxides and alkali metal amides convert any allene or 1,2-dienecompounds to the corresponding acetylenic compound. Furthermore, alkalimetal amides, and especially sodamide (sodium amide) not only favors theformation of acetylenic groups but also favors the making of terminalacetylenic groups, i.e., the acetylenic group is between the first andsecond carbon atom, even though the initial acetylenic group is betweenthe second and third carbon atom.

The use of various dehydrohalogenating agents, the effect on theparticular product obtained, the conditions to be used, etc., are wellknown in the art. See for example, Method 43 in the above reference bookby Romeo B. Wagner and Harry D. Zook and the references cited therein,the book Acetylenes and Allenes by Thomas F. Rutledge, Reinhold BookCorporation, New York (1969), especially pages 35 to 57, the bookAcetylenic Compounds by Thomas F. Rutledge, Reinhold Book Corporation,New York (1968), especially pages 22-44, the book The Chemistry ofAlkenes edited by Saul Patai, Interscience Publishers, New York (1964),especially Chapter 13, by H. Fisher and the book Chemistry of Acetylenesedited by Heinz G. Viehe, Marcel Dekker, New York (1969), especiallyChapter 2. The above references and their footnote references hereby areincorporated by reference for their teaching as to the types ofchlorinated materials and dehydrohalogenated products obtained and theeffect of reagents, reaction conditions and other parameters that governthe types of products.

The reaction of dichlorophosphoranes is broadly applicable to allketones for preparing halogenated compounds which are useful, per se, inorganic synthesis or for preparing acetylenic derivatives bydehydrohalogenation. However,-it is obvious from what has been saidabove that the reaction becomes more complex unless thereis at least onemethyl group attached directly to the ketonic carbonyl group, i.e., theketone can be described as a methyl ketone or as a molecule having aketonic acetyl group. Furthermore, the acetylenic compounds prepared bydehydrohalogenation of the chlorinated compounds, although usefulchemical compounds because of the acetylenic group, cannot be used asmonomers for preparing the polyacetylenes since such monomers must haveterminal acetylenic groups, i.e., there must be a hydrogen on theterminal carbon atom which is joined to the adjacent carbon atom withthe acetylenic triple bond (C CH).

For these reasons, my invention, in its preferred embodiments, islimited to those ketones wherein the ketonic carbonyl group is presentas an acetyl group, hereinafter referred to .as ketonic acetyl group.There may be one or more such ketonic acetyl groups present in themolecule but for simplicitys sake, availability of starting materials,and desirability of the resulting chlorine-containing derivatives andacetylenic derivatives thereof, the compounds generally have no morethan three and usually 'one or two ketonic acetyl groups. The balance ofthe molecule, as long as it is non-reactive with any of the reactant orproduct groups, can be any desired moiety. However, from a practicalstandpoint it has no more than carbon atoms and is selected from thegroup consisting of hydrocarbon, halohydrocarbon, aryl ether andhaloaryl ether, i.e., the balance of the molecule can be aliphatichydrocarbon, either saturated or having olefinic or acetylenicunsaturation, preferably saturated or olefinic, aryl, aliphatichydrocarbon substituted aryl, aryl substituted aliphatic hydrocarbon,the same hydrocarbons wherein one or more of the hydrogens have beenreplaced with a halogen, preferably chlorine, and, in the case ofpolynuclear aryls and haloaryls, wherein two or more aromatic rings arejoined together they can be joined together with an intervening oxygenatom in the form of aryl ethers and haloaryl ethers.

Typical, but not limiting examples of ketones which I may use are:acetone, methyl ethyl ketone, methyl npropyl ketone, methyl isopropylketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl s-butylketone,

methyl t-butyl ketone, methyl n-amyl ketone, methyl isoamyl ketone,4-methyl-2-hexanone, 3-methyl-2-hexanone, 3-ethyl-2-pentanone, methylneopentyl ketone, methyl t-amyl ketone, 3,4-dimethyl-2-pentanone, 3-acetyldibenzofuran, methyl n-hexyl ketone, methyl isohexyl ketone,3-methyl-2-heptanone, 3,4-dimethyl- 2-hexanone, 4-ethyl-2-hexanone,3-methyl-3-ethyl-2- pentanone, methyl n-heptyl ketone,4-methyl-2-octanone, 3-methyl-3-ethyl-2-hexanone, methyl n-octyl ketone,methyl n-decyl ketone, methyl n-undecyl ketone, methyl n-heptadecylketone, Z-heneicanone, methyl cyclopropyl ketone, methyl cyclobutylketone, methyl cyclopentyl ketone, Z-methyl-S-'ethylcyclo-pentanone,methyl cyclohexyl ketone, cyclohexylacetone,a-methyl-a-cyclopentylacetone, acetophenone, methyl benzyl ketone,o-methylacetophenone, mmethylacetophenone, p-methyl-acetophenone,benzylacetone, 3-phenyl-2-butanone, 2-aceto-pcymene,o-ethylacetophenone, m-ethylacetophenone,

p-ethyl-acetophenone, 2,4-dimethylacetophenone, 2,5-dimethylaceto-phenone, 3,4-dimethylacetophenone,3,S-dimethylacetophenone, 3-phenyl-2-pentanone, 4- phenyl- 2-pentanone,5-phenyl-2-pentanone, 3-methyl- 3-phenyl-2-butanone,3-methyl-4-phenyl-2-butanone,

2,4,5-trimethylacetophenone, 2,4,6- trimethylacetophenone,S-acetylindane, mesitylacetone, p-n-butylacetopheonone,p-isobutylacetophenone, p-s-butylacetophenone, p-t-butylacetophenone,Z-methyl-S-isopropylacetophen0ne, acetodurene, acetoisodurene,acetoprehnitene, methyl a-naphthyl ketone, methyl B-naphthyl ketone, 6-

acetyltetralin, p-n-amylacetophenone, pisoamylacetophenone,p-s-amylaceto-phenone, p-tamylacetophenone, acetopentamethylbenzene, 4-phenylhexahydroacetophenone, p-cyclohexylacetophenone, 2-acetylbiphenyl,3-acetylbiphenyl, 4- acetylbiphenyl, I l-acetoacenaphthene,benzylacetophenone, a,a-diphenylacetone, 2acetylfluorene,9-acetylfluorene, l-acetylphenanthrene, 2- acetylphenanthrene,3-acetylphenanthrene, 9- acetylphenanthrene, 9-acetylanthracene,acetylacetone, acetonylacetone, methyl-diacetylmethane,triacetylmethane, 3-methyl-2,5-hexanedione,

one, 2,2-dimethyl-3-hexyn-5-one, l-cyclohexyl-lbutyn-3-one,fluoroacetone, chloroacetone, bromacetone, l,l ,l-tribromoacetone, 1,1,l trifluoroacetone, 1,1,l-trichloroacetone, methyl achloro-ethylketone, methyl a-bromoethyl ketone, methyl B-chloroethyl ketone, methyla,B-dichloroethyl ketone, 2-bromo-2-penten-4-one, 4-bromo-3-octen-2-one, methyl a-chloro-n-propyl ketone, methyl ychloro-n-propyl ketone,methyl a-bromo-n-propyl ketone, methyl a-chloroisopropyl ketone, methyl(1- bromoisopropyl ketone, 4-brom0-5-chloro-2-pentanone,-chloro-2-pentanone, 3,4-dibromo-3-methyl- 2-butanone,6-bromo-2-hexanone, 2-chloro-2-methyl- 4-pentanone,3,4-dibromo-3-methyl-2-pentanone, 3- bromo-l,3-hexadien-5-one,3-bromo-2-heptanone, 1- bromo-6-heptanone, 3-methyl-6-bromo-2-hexanone,3,4-dimethyl-4-chloro-2-pentanone, methyl a-bromocyclohexyl ketone,l-acetyl-l ,2 -dibromo-cyclohexane,

o-chloroacetophenone, o-bromoacetophenone, mchloroacetophenone,m-bromoacetophenone, miodoacetophenone, pfluoroacetophenone,pchloroacetophenone, p-bromoacetophenone, piodoacetophenone,a-chloro-a-phenylacetone, abromo-a-phenyl-acetone, o-chlorobenzyl methylketone, p-chlorobenzyl methyl ketone, p-acetobenzyl bromide,m-trifluoromethylacetophenone, 4-phenyl-3- chloro-2-butanone,4-phenyl-3-bromo-2-butanone, benzalacetone dichloride, benzalacetonedibromide, pphenoxy-acetophnone, p-(chlorophenoxy)acetophenone,acetylferrocene, etc.

The course of the reaction is readily followed by nmr spectroscopynoting the disappearance of the carbonyl group and the appearance of thea,a-dichloroethyl group, the a-chlorovinyl group and, where produced,the a-chloroethylidene group. One might expect that the a-chlorounsaturated groups come from dehydrohalogenation of the diehloroethylgroups. However, I have found that, in addition to being formed bydehydrohalogenation of the diehloroethyl group, they are formeddirectly, since in monitoring my reactions, l have been able to detectthe unsaturated chlorine-containing groups as early as the saturatedchlorine-containing groups, and the concentration of both increases withtime until late in the reaction when essentially all of the ketone hasreacted. Then the unsaturated chlorine-containing groups continue toincrease especially when the reaction is carried out at elevatedtemperatures, at the expense of the (1,0:- dichloroethyl groups. Thereis no necessity for carrying out the reaction after all of the ketonicacetyl groups have reacted with the dichlorophosphorane. However, if theproducts are to be dehydrohalogenated to the acetylenic compounds, or itis desired to produce the achlorovinyl or a-chloro-ethylidene compounds,then the amount of dehydrohalogenating agent can be conserved bycontinuing the reaction to dehydrohalogenate the a,a-dichloroethylgroups, which occurs merely by heating the reaction mixture, to thedesired extent or until no more dehydrohalogenation occurs by thismeans.

In order that those skilled in the art may better un derstand myinvention the following examples are given by way of illustration andnot by way of limitation. In all of the examples, parts are by weightunless stated otherwise and temperatures are given in degreescentigrade.

EXAMPLE 1 A solution of 8.11 g. of m-diacetylbenzene and 27.82 g. oftriphenylphosphine oxide in 50 ml. of anhydrous acetonitrile was placedin a reaction vessel equipped with a water-cooled condenser, stirrer,thermometer, and gas inlet tube. While cooling the reaction vessel witha water bath, phosgene was introduced into the vapor phase of thereaction vessel from where it was rapidly dissolved in the liquid phasecausing an exothermic reaction with evolution of carbon dioxide. Afterapproximately 10 minutes, the evolution of carbon dioxide had ceased andthe flow of phosgene was stopped. The reaction mixture was heated toreflux while permitting any excess phosgene to escape through the top ofthe condenser which was open to the atmosphere through a drying tubefilled with desiccant. After 18.5 hours of heating at reflux, an nmrspectrum of the reaction mixture showed that it contained muchtriphenylphosphine oxide, some dichlorotriphenylphosphorane, somehydrogen chloride and that the ratio of a-chlorovinyl groups to acetylgroups attached to an aromatic nucleus was in the ratio of 86/14.

While cooling the reaction mixture in the cold water bath, phosgeneagain was introduced, until carbon dioxide evolution ceased, toreconvert the triphenylphosphine oxide to dichlorotriphenylphosphorane,which again required about 10 minutes. The system again was heated toreflux for an additional 8 hours at which time the nmr spectrum showedthe complete absence of acetyl groups and the ratio of a-chlorovinylgroups to triphenylphosphorus moieties was ill which is the theoreticalratio for a percent yield of mbis(a-chlorovinyl)benzene fromm-diacetylbenzene.

The reaction mixture was mixed with 250 ml. of water to which 20 g. of50 percent aqueous sodium hydroxide was added to hydrolyze all of theremaining dichlorotriphenyl-phosphorane to triphenylphosphine oxide.After adding 250 ml. of chloroform and vigorously shaking the mixture,the aqueous layer was separated and discarded. The organic layer waswashed with water and dried over anhydrous magnesium sulphate andfiltered. A sample of the filtrate was analyzed by vapor phasechromatography and found to contain only the two expected products.

All of the solvent was removed from the filtrate under vacuum, first atroom temperature and finally at 50 C., leaving 37.6 g. ofa mixture ofasolid and liquid. This was dissolved in 200 ml. of carbon tetrachlorideby heating at 50 C., after which 500 ml. of pentane was added to producea copious precipitate which was removed by filtration and washed twotimes with 100 ml. portions of pentane. After removing the last tracesof pentane by heating in a vacuum desiccator at approximately 60 C.,there was obtained 24.3 g. of triphenylphosphine oxide, melting pointl55-l56.5 C. (literature melting point 156 C.). Comparison of thisproduct with an authentic sample of triphenylphosphine oxide by vaporphase chromatography and infrared spectroscopy showed them to beidentical. Complete removal of the solvent under vacuum from thecombined carbon tetrachloride-pentane filtrates from above andtrituration of the residue with 300 ml.

of pentane gave an additional 1.81 g. of triphenylphosphine oxide sothat the total recovery was 26.11 g., or 94 percent of the theoreticalamount based on the starting quantity. The pentane filtrate from thelatter trituration was treated with charcoal to remove a small amount ofcolor, filtered and freed of solvent under vacuum. There was obtained9.07 g. ofa liquid product which was shown by vapor phasechromatography, nmr spectroscopy and mass spectroscopy to bem-bis(achlorovinyl)benzene containing 0.59 g. of triphenylphosphineoxide which could be removed by further purification. However, since itdoes not interfere with the dehydrohalogenation of this compound todiethynylbenzene, as illustrated hereinafter, complete removal is onlydesirable for economic reasons. Where this is desired it is much easierto do this in the continuous process which will be illustratedhereinafter.

EXAMPLE 2 Sodamide was made by adding 0.25 g. of sodium metal and 0.1 g.of hydrated ferric nitrate to approximately 200 ml. ofliquid ammonia ina 1000 ml. roundbottomed flask equipped with a solid carbondioxideacetone condenser. After 5 minutes, the blue color was destroyedby passing air into the reaction mixture after which 5.75 g. of sodiummetal was added over a period of 5 minutes and the reaction permitted tocontinue until the blue color had completely disappeared from the graysuspension of Sodamide in the liquid ammonia. A solution of 8.77 g. ofthe m-bis(a-chloroviny1)benzene from Example 1, in 100 ml. of anhydrousether was added dropwise over a period of minutes. After an additional 3hour period, 100 ml. of water and 50 ml. of pentane were added and mostof the ammonia was allowed to evaporate. An additional 150 ml. of waterand ISO ml. of pentane were added and the solution was neutralized withaqueous concentrated hydrochloric acid. After separating the acid layer,the organic layer was extracted with water and dried over anhydrousmagnesium sulphate. After filtering, solvent removal under vacuum gave4.68 g. (90 percent isolated yield) of m-diethynylbenzene which wasidentified by comparison with an authentic sample by vapor phasechromatography and nmr spectroscopy.

Acetophenone was converted to a-chlorostyrene by using 12.01 g. ofacetophenone in place of the mdiacetylbenzene in Example 1. Likewise,the achlorostyrene can be converted to phenylacetylene by the procedureof Example 2. Alternatively, both the achlorostyrene and them-bis(a-chlorovinyl)benzene can be dehydrohalogenated by using otherknown dehydrohalogenating agents in place of sodamide, for example,aqueous or alcoholic sodium or potassium hydroxide, etc.

EXAMPLE 3 Example 1 was repeated except twice the amount (55.64 g.) oftriphenylphosphine oxide was used to provide a 1 molar excess of thedichlorotriphenylphosphorane after reaction with the phosgene. Sampleswere taken during the reaction period at reflux and examined by vaporphase chromatography, infrared and nmr spectroscopy. After approximately7 hours, the reaction between the ketone and phosphorane wereessentially complete since these analyses showed the absence of theacetyl group. At this point in time, the ratio of os-chlorovinyl toa,a-dichloro-ethyl groups was in the ratio of 93/7. Further heating atreflux caused a gradual shift in this ratio so that it was approximately95/5 after 9.5 hours, 97/3 after 12 hours, 98/2 after 14 hours and 99/1after 19 hours. Since both groups are readily dehydrohalogenated to theethynyl group, the cost of this additional heating must be balancedagainst the additional cost of the dehydrohalogenating agent required todehydrohalogenate the a,a-dichloroethyl group rather than thea-chlorovinyl group.

The reaction mixture was extracted with three 500 ml. portions ofpentane and the combined pentane fractions, in turn, were extracted with300 ml. of methanol containing 50 ml. of aqueous one-normal hydrochloricacid to remove a small amount of triphenylphosphine oxide. The pentanephase was dried with calcium oxide and anhydrous magnesium sulphateafter which it was filtered and freed of solvent under vacuum to give8.85 g. of m-bis(a-chlorovinyl)-benzene containing 0.44 g. oftriphenylphosphine oxide. Dilution of the acetonitrile solution withwater precipitated 52.23 g. of triphenylphosphine oxide while 2.01 g.was recovered in the same manner from the acidic aqueous methanolextract. Thus there was recovered 54.68 g. (99 percent) of the initialtriphenylphosphine oxide which can be reused.

In a similar manner, p-diacetylbenzene was converted top-bis(a-chlorovinyl)benzene and acetylferrocene was converted toachlorovinylferrocene. When this example was repeated but benzene usedin place of the acetonitrile, the reaction was heterogeneous throughoutmost of the reaction which was extremely slow in comparison to thehomogeneous reaction using acetonitrile. Furthermore, a separation ofthe products were much more difficult since the extraction with pentanecould not be used because of its miscibility with benzene.

EXAMPLE 4 This example illustrates the continuous process for conversionof the ketonic acetyl compound to the chloro derivatives. A suspensionof 55.64 g. of triphenylphosphine oxide in 100 ml. of anhydrousacetonitrile was reacted with phosgene while stirring and cooling untilthe evolution of carbon dioxide ceased. During this period, the reactionmixture became completely homogeneous as thedichlorotriphenyl-phosphorane formed. it was heated at reflux for onehour to expel any excess phosgene. After cooling the solution to roomtemperature, 8.11 g. of m-diacetylbenzene was added and the solutionheated at reflux for 22 hours. After cooling, the reaction mixture wasextracted with three 500 ml. portions of pentane and in turn thecombined pentane phases were extracted with two portions of 300 ml. ofmethanol containing 50 ml. of aqueous one-normal hydrochloric acid, fromwhich was recovered 3.32 g. of triphenylphosphine oxide. After washingthe pentane phase with one 500 ml. portion of water, it was dried over amixture of calcium oxide and anhydrous magnesium sulphate, filtered andthe solvent evaporated under vacuum to give an 86 percent yield ofproduct which was 95.2 percent m-bis(achlorovinyl)benzene and 4.8percent m-(a,adichloroethyl)-a-chlorostyrene.

The acetonitrile layer remaining after extraction with pentane whichcontained triphenylphosphine oxide and dichlorotriphenylphosphorane wasbrought up to the initial volume by the addition of 40 ml. of anhydrousacetonitrile. The triphenylphosphine oxide which had been recovered fromthe methanol extract was not replenished, since at this point in time,the amount had not yet been determined, but preferably, should be addedback at this point. Phosgene was introduced into this solution toreconvert all of the triphenylphosphine oxide produced in the abovereaction back to dichlorotriphenyl-phosphorane. After refluxing one hourto remove any excess phosgene, 8.11 g. of mdiacetylbenzene was added andthe solution refluxed for 22 hours. The above extraction procedure wasrepeated giving an 88% yield of a chlorinated mixture which was 86.6%m-bis(a-chlorovinyl)benzene, 11.9% m-(a,a-dichloroethyl)a-chlorostyreneand 1.5% bis(a,a-dichloroethyl)benzene. Again 3.33 g. oftriphenylphosphine oxide was recovered from the acidic methanol extract.

When the reaction mixture described above, which is free of excessphosgene, is heated in a glass-lined autoclave at 180 C., them-diacetylbenzene is converted in greater than 99 percent yield tom-bis(a-chlorovinyl)benzene in 1 hour.

EXAMPLE Using a 0.5 molar excess of dichlorotriphenylphosphoraneprepared by the procedure described in Example 4, the followingreactions were carried out with it and various other ketonicacetyl-containing compounds. Reactions at room temperature were carriedout in closed reaction vessels with no stirring being necessary becausethe solutions were homogeneous at all times. At elevated temperatures,the apparatus described in Example 1 was used. Acetone in a 96 hourreaction at room temperature gave a 63 percent yield of 2-chloropropeneand a 5 percent yield of 2,2- dichloropropane with no evidence of anyby-products. Methyl ethyl ketone in a 96 hour reaction at roomtemperature gave a yield of 2-chloro-l-butene, a 42 percent yield of2-chloro-2-butene and a 24 percent yield of 2,2-dichlorobutane with noevidence of any byproducts. in a reaction at 84 C. for 19 hours, methylethyl ketone gave a 19 percent yield of 2-chloro-1-butene, a 64 percentyield of 2-chloro-2-butene and a 10 percent yield of 2,2-dichlorobutane.Acetylacetone in a 19 hour reaction at 84 C. gave an 8 percent yieldof4- chloro-3-penten-2-one, an 83 percent yield of 2,4-dichloro-l,3-pentadiene and a 5 percent yield of 2,2,4-trichloro-4-pentene.

Because of the volatile product of this reaction, the top of thewater-cooled reflux condenser was connected to a receiver cooled with asolid carbon dioxideacetone bath when acetone was reacted at 84 C. for19 hours. During this time an 85 percent yield of pure 2- chloropropenedistilled into the receiver. The reaction mixture remaining in thereactor contained a 6 percent yield of 2,2-dichlororpropane with noevidence of any by-products. This product is readily isolated and thetriphenylphosphine oxide reused as described in Example 4. Replacing thereflux condenser with a 10 cm. Vigreux column, and a water-cooleddistillation condenser, methyl vinyl ketone (3-buten-2-one) was reactedat 84 C. for 4 hours. During this time, a 32 percent yield of 2-chloro-l,3-butadiene distilled at 58.5-6 0.5 C. (literature 59.4 C.) along witha small amount of acetonitrile. The residual reaction mixture containeda 49 percent yield of 1,3-dichloro-2-butene and a 10 percent yield of1,3-dichloro-3-butene with no evidence of any by-products. These twoproducts are readily isolated and the triphenylphosphine oxide reused asdescribed in Example 4.

EXAMPLE 6 The purpose of this example is to illustrate the effect ofsolubility and of the R group on reactivity. in order to accomplishthis, the reaction conditions were chosen so that no reaction wascomplete so that the degree of completion is a measure of the relativereactivities. Based on what has been taught previously, it will bereadily apparent that changes can be made to improve the yield of anyone of the reactions. For example, Examples 3 and 4 show how theseteachings have been applied to improving the yields when usingdichlorotriphenylphosphorane.

The following reactions were carried out for 17 hours at 84 C. (reflux)using acetonitrile as the solvent and acetophenone as the ketone which,under the reaction conditions used, produces a-chlorostyrene as the soledetectable product so that it was used in determining yields.

in all cases, except for the dichlorotri-ptolylphosphorane, thephosphoranes were made in situ by passing phosgene into the solution ofthe phosphine oxide until evolution of carbon dioxide was complete afterwhich the solution was refluxed for one hour to expel any excessphosgene. The dichlorotri-ptolylphosphorane was made by chlorination oftri-ptolylphosphine dissolved in acetonitrile at room temperature untilthe yellow color showed excess chlorine was present. This excesschlorine was removed by refluxing the solution for one hour.

Table I shows the amount of reactants and the yield of a-chlorostyrene.Except where footnoted, the solutions were homogeneous both at roomtemperature and at the reaction temperature.

(a) Heterogeneous at room temperature, soluble at reaction temperature.

(b) Heterogeneous both at room ture.

temperature and at reaction tempera- Although the above examples haveillustrated many modifications that can be made in this invention, othervariations will be readily apparent to those skilled in the art. Forexample, other solvents may be used in place of the acetonitrile andother phosphine oxides can be used in place of the particular phosphineoxides used, but would be more expensive and offer no advantage sincethey would be no more effective. Howi I ever, stibene oxides, R SbO, andarsine oxides, R AsO,

can not be used in place of the phosphine oxides, nor can theircorresponding dichlorides be used in place of the dichlorophosphoranes.The reaction can be hastened still further, by use of a hydrogen halideacceptor for the hydrogen halide evolved during the reaction, forexample, a tertiary amine which is stable under the reaction conditions.These amines also aid in conversion of the gem-dichloride products tothe chlorine containing substituents selected from the group consistingof a-chlorovinyl, a-chloroethylidene and a,a-di-chloroethyl substituentsin a ketone containing at least one said acetyl substituent as theketonic moiety, the balance of the molecule having up to 20 carbon atomsand being selected from the group consisting of hydrocarbon,halohydrocarbon, aryl ether and haloaryl ether, which comprises reactingsaid ketone with a phosp'horane having the formula R PCl 'where each Ris independently selected from the group consisting of C alkyl, phenyl,lower alkyl substituted phenyl, halophenyl, phenoxyphenyl and naphthyl.

2. The process of converting ketonic acetyl substituents to ethynylsubstituents which comprises converting the acetyl substituentsto'chlorine containing substituents by the process of claim 1 andthereafter dehydrohalogenating the chlorine containing substituents toethynyl substituents with a dehydrohalogenating agent underdehydrohalogenating conditions.

3. The process-of using phosgene to convert ketonic acetyl substituentsto chlorinecontaining substituents which comprises reacting phosgenewith a phosphine oxide having the formula R PO to produce thedichlorophosphorane which then is reacted with a ketone in the processof claim 1.

4. The process of using phosgene to convert ketonic acetyl substituentsto ethynyl substituents which comprises reacting phosgene with aphosphine oxide having the formula R PO to produce thedichlorophosphorane which then is used in the process of claim 2.

5. The process of claim 1 wherein the ketone is an acetyl benzene.

6. The process of claim 1 wherein the ketone is mdiacetylbenzene,p-diacetylbenzene or mixtures thereof.

7. The process of claim 1 wherein the ketone is an alkyl methyl ketone.

8. The process of claim 1 wherein the ketone is acetone.

9. The process of claim 1 whereln the ketone is an alkenyl methylketone.

10. The process of claim 1 wherein the ketone is methyl vinyl ketone.

11. The continuous process for using phosgene to convert ketonic acetylsubstituents to chlorine containing substituents which comprises (a)reacting phosgene with a phosphine oxide having the formula R PO toproduce a dichlorophosphorane having the formula R PCl (b) using thedichlorophosphorane of (a) in the process of claim 1, using acetonitrileas the solvent for the ketone, (c) extracting the reaction producthaving chlorine containing substituents from the reaction mixture with aliquid alkane immiscible with acetonitrile, (d) isolating theacetonitrile layer containing the phosphine oxide and (e) recycling theacetonitrile layer to process step (a).

12. The process of claim 11 wherein the each R is phenyl.

13. The process of claim 12 wherein the ketone is an acetylbenzene.

14. The process of claim 12 wherein the ketone is mdiacetylbenzene,p-diacetylbenzene or mixtures thereof.

15. The process of claim 12 wherein the ketone is an alkyl methylketone.

16. The process of claim 12 wherein the ketone is acetone.

17. The process of claim 12 wherein the ketone is an alkenyl methylketone.

18. The process of claim 12 wherein the ketone is methyl vinyl ketone.

1. The process of converting acetyl substituents to chlorine containingsubstituents selected from the group consisting of Alpha -chlorovinyl,Alpha -chloroethylidene and Alpha , Alpha -di-chloroethyl substituentsin a ketone containing at least one said acetyl substituent as theketonic moiety, the balance of the molecule having up to 20 carbon atomsand being selected from the group consisting of hydrocarbon,halohydrocarbon, aryl ether and haloaryl ether, which comprises reactingsaid ketone with a phosphorane having the formula R3PCl2 where each R isindependently selected from the group consisting of C1 20 alkyl, phenyl,lower alkyl substituted phenyl, halophenyl, phenoxyphenyl and naphthyl.2. The process of converting ketonic acetyl substituents to ethynylsubstituents which comprises converting the acetyl substituents tochlorine containing substituents by the process of claim 1 andthereafter dehydrohalogenating the chlorine containing substituents toethynyl substituents with a dehydrohalogenating agent underdehydrohalogenating conditions.
 3. The process of using phosgene toconvert ketonic acetyl substituents to chlorine containing substituentswhich comprises reacting phosgene with a phosphine oxide having theformula R3PO to produce the dichlorophosphorane which then is reactedwith a ketone in the process of claim
 1. 4. The process of usingphosgene to convert ketonic acetyl substituents to ethynyl substituentswhich comprises reacting phosgene with a phosphine oxide having theformula R3PO to produce the dichlorophosphorane which then is used inthe process of claim
 2. 5. The process of claim 1 wherein the ketone isan acetyl benzene.
 6. The process of claim 1 wherein the ketone ism-diacetylbenzene, p-diacetylbenzene or mixtures thereof.
 7. The processof claim 1 wherein the ketone is an alkyl methyl ketone.
 8. The processof claim 1 wherein the ketone is acetone.
 9. The process of claim 1wherein the ketone is an alkenyl methyl ketone.
 10. The process of claim1 wherein the ketone is methyl vinyl ketone.
 11. The continuous processfor using phosgene to convert ketonic acetyl substituents to chlorinecontaining substituents which comprises (a) reacting phosgene with aphosphine oxide having the formula R3PO to produce a dichlorophosphoranehaving the formula R3PCl2, (b) using the dichlorophosphorane of (a) inthe process of claim 1, using acetonitrile as the solvent for theketone, (c) extracting the reaction product having chlorine containingsubstituents from the reaction mixture with a liquid alkane immisciblewith acetonitrile, (d) isolating the acetonitrile layer containing thephosphine oxide and (e) recycling the acetonitrile layer to process step(a).
 12. The process of claim 11 wherein the each R is phenyl.
 13. Theprocess of claim 12 wherein the ketone is an acetylbenzene.
 14. Theprocess of claim 12 wherein the ketone is m-diacetylbenzene,p-diacetylbenzene or mixtures thereof.
 15. The process of claim 12wherein the ketone is an alkyl methyl ketone.
 16. The process of claim12 wherein the ketone is acetone.
 17. The process of claim 12 whereinthe ketone is an alkenyl methyl ketone.